Automatic chemical analyzer and controller

ABSTRACT

A method and apparatus for the automatic monitoring, analyzing and controlling of the etch rate and chemical concentration of a chemical-milling solution responsive to pH values at first and second equivalence points for both caustic soda and inhibitor.

United States Patent inventors Appl. No.

Filed Patented Assignee CONTROLLE 2 Claims, 2 Drawing Figs.

11.8. C1. 156/345, 156/19, 156/22, 23/230 A, 23/253 A, 134/10, 134/57. 137/93 Int. Cl ..G0ln 31/16,

Ewald J. Bielefeld, Jr.

Benbrook;

Maurice J. Puma, Fort Worth, both of Tex. 766,161

Oct. 9, 1968 Sept. 21, 1971 General Dynamics Corporation AUTOMATIC CHEMICAL ANALYZER AND czgrups, ogsd 11/08 [50] Field ofSearch 156/19, 345, 22; 137/93; 134/10, 57; 23/230, 230 A, 253

[56] References Cited UNITED STATES PATENTS 2,063,140 12/1936 Allison 23/230 A 3,073,682 1/1963 Lindsley 23/230 A Primary Examiner-Robert F. Burnett Assistant Examiner-R. J. Roche Attorney-Charles C. M. Woodward ABSTRACT: A method and apparatus for the automatic monitoring, analyzing and controlling of the etch rate and chemical concentration of a chemical-milling solution responsive to pH values at first and second 729t ca s q and i i equivalence points for sunomo ACID sow-non AUTOMATIC CHEMICAL ANALYZER AND CONTROLLER The present invention relates generally to a method and apparatus for automatically sampling, analyzing and controlling chemical-milling solutions.

More particularly this invention is directed to a process and related instrumentation for sampling, analyzing and controlling the relative strength of aluminum chemical milling solutions.

PRIOR ART In the past, etchant solution analyses have been performed by manually sampling and analyzing the etchant solution. Results of the analysis required manual computation to determine necessary corrective action-such as tank drainoff or replenishment of depleted chemicals-both of which corrections were also, of necessity, performed manually.

Several disadvantages are inherent in this prior art operation which the present invention obviates. The manual method is time-consuming, and the lag time between analysis and corrective action prevents the maintenance of the precise concentrations necessary for a constant and uniform etch rate. The invention also permits the elimination of human errors and prevents interruption of production during the period in which corrective action is being taken.

BRIEF SUMMARY OF THE INVENTION This invention affords an automatic chemical sampler, analyzer and controller which provides a method and means by which chemical-milling solutions may be automatically monitored, analyzed and controlled during all phases of chemical milling or etching through a coordination and metering of material pumps and pH meters which are set at desired, predetermined values, variances from these values beyond predetermined critical limits at either or both equivalence points initiating signals which in turn activate control valves at the chemical-milling tanks, corrective action being taken constantly and automatically, thereby maintaining constant chemical concentrations and etch rate, which in context of the often critical degree" of etch in present applications is of prime importance.

The invention will be readily understood by those versed in the art when taken in context of the following specification and related drawings, wherein:

FIG. 1 is a typical titration curve for an aluminum etch tank showing the two equivalence points resulting from the neutralization of the sample with a standardized acid solution; and

FIG. 2 is a schematic plan view of a typical production tank constructed in accordance with the present invention and showing the relationship of the various components to each other and to the system.

The process for carrying out the invention is applicable to substantially all solutions of this type, however, as an exemplary and preferred process the analysis of caustic soda and sodium aluminate is described herein since it is the most common process employed by the industry.

Referring first to FIG. 1, the analysis of N, (caustic soda) and N (sodium aluminate) may be described briefly as follows:

A 5 milliliter sample of etchant is taken and neutralized to a pH of 11.5 with one normal acid. The number of milliliters of one normal acid required to reach a pH of 11.5 on a 5 milliliter sample is defined to be the N value, FIG. 1, and is a measure of the free caustic soda. Upon adding more acid the sodium aluminate is converted to aluminum hydroxide with another change in pH from 11.5 to 8.5. The number of milliliters of one normal acid required to, lower the pH from 1 1.5 to .8.5 on a 5 milliliter sample is defined to be the N value and is a measure. of the inhibitors (primarily'sodiumaluminate).

The N and N equivalence points are shown in the titration curve 110.

Referring now to FIG. 2, a system constructed according to the present invention is shown as generally comprising an etch tank section 210 and a control section 212. Etch tank section 210, wherein the actual etching is accomplished, is controlled by control section 212 which accomplishes the pH analysis and performs the necessary corrective action based on the analysis. If standard acid solution 214 and the etch tank solution 216 are allowed to flow via dual metering pumps 218, 220 at a constant rate, and mixed with water in the mixing chambers 252, 254, to avoid excessive buildup of heat, a neutralization reaction occurs. If the acid in the solution 214 is exactly equivalent to the caustic soda in the etch solution 216, the resultant pH will be 1 1.5 as determined by the titration curve, FIG. I. A pH of less than l 1.5 would mean an acid condition or a caustic soda deficiency requiring corrective action, i.e., addition of caustic soda to the etchant solution 216 and is readily detected by use of the present invention because the caustic exhibits a sharp change in pH value at the first equivalence (N point. On the other hand, a pH of more than 1 1.5 would mean an alkaline condition or an excess of caustic soda requiring no corrective action. Similar but opposite pH changes occur for the sodium aluminate (inhibitor) analysis with corrective action (drainoff) being taken above 8.5 pH, also readily detected because the inhibitor exhibits a sharp change in pH at the second equivalence (N point.

A typical cycle for an etch tank solution analyzer and controller is described below. Although only one tank system is described in the interest of clarity, it is apparent that any number may be controlled by expanding the system. Briefly, prior to being electrically activated, the unit is set at the zero point on the stepping relay 222, FIG. 2. Relays 224, 226 are open, and all addition valves 228, drain valves 230 and sample valves 232 are closed. The master switch activates both pH meters 234, 236, master timer 238, and metering pumps 218, 220. The water flow is constant and is manually set at the water injection meters 256, 258. The master timer 238 is preset to pulse stepping relay 222 which in turn controls the entire sequence of operations. The odd numbered contacts I, 3, 5, 7 and 9 on stepping relay 222 are sample purging steps where no pH meter signals are transmitted. The continuity of numbers on the stepping relay 222 indicates that it controls more than one tank, however, since this specification shows the operation of only one tank, there are only two settings pertinent here, positions 1 and 2. The zero point indicates the inoperative or shutoff position. Master timer 238 is preset to hold stepping relay 222 on position number 1" contact for sufficient time to purge the solution flow system. Position number 2 on stepping relay 222 activates relays allowing pH meter signals to pass to timers 240, 242, the former controlling addition valve 228 and the latter drain valve 230, the pH meter signals being responsive to any variation in equivalence points for which the pH meters are set. The dwell time on position number 2 contact is only long enough for the pH meter to signal the appropriate timers should corrective action be necessary. Thus, each etch tank is analyzed and corrective action taken in sequence, automatically and continuously.

It should be noted that the water to mixing chambers 252, 254 is required to dissipate the heat of reaction and does not affect the resultant pH (hydrogen ion concentration).

The cycle begins as above noted, by purging control section 212, in which master timer 238 pulses stepping relay 222 to contact point number 1. As seen in FIG. 2, sample solenoid valve 232 to etch tank 246 is opened allowing a sample of etchant 216 from a continuously flowing etchant stream flowing from the etch tank 246 through flow pump 248 to continuous drain 250, to be diverted through solenoid sample valve 232, which etchant is then pumped through metering pumps 218, 220 to mixing chambers 252, 254 where the metered sample of etchant solution is thoroughly mixed with 36 noracid (H solution and diluted with water controlled by water injection meters 256, 258 before passing to flow chambers 260, 262 where the. pH measurements are made.

The sample and acid flow rates are preset in metering pumps 218, 220 which are adjusted to be compatible with the desired equivalence points as indicated at N N of FlG. 1. Again referring to FIG. 2, metering pumps 218, 220 pump etchant and standard acid solutions continuously while the solution controller device is on and are not controlled or affected by any automatic action of the solution controller device. Concurrently with the above, when the solution purging period is complete and master timer 238 pulses stepping relay 222 to contact point 2," relays 224, 226 are closed responsive to contact point 2" This completes the circuits from the pH meters 234, 236 to the timers 240, 242.

The pH meters 234, 236 read the pH of the solutions flowing through flow chambers 260, 262 continuously, but signals are not transmitted unless the pH is below the N, or above the N set points. For example, the N flow chamber 260 should have a pH reading above 1 1.5 to be in proper concentration range. An etch solution depleted in caustic soda will not use all of the allotted acid, resulting in a lower pH reading which indicates a more acid condition. Should the pH fall below 11.5 the N, pH meter 234 is preset to send an electrical signal through closed relay 226 to timer 240 which in turn controls caustic soda addition valve 228 to etch tank 246. This allows replenishment of caustic soda to etch tank 246 for a preset time period and is independent of other action during the cycle. Similarly, the N pH meter 236 should have a pH reading of less than 8.5 to be in proper range. A solution having a higher than desired inhibiting content (sodium aluminate) will have a higher pH than 8.5 since the increase of sodium aluminate will use up the neutralizing acid. A pH reading greater than the preset 8.5 will cause the N pH meter 236 to send an electrical signal through relay 224 which in turn activates timer 242 controlling drain valve 230 on etch tank 246. This allows etch solution 216 in etch tank 246 to drain for a preset time, thereby reducing the excess aluminum buildup. Timers 240, 242 automatically reset for the next cycle and a constant level control 264 is independently activated to allow addition of water through valve 266 to etch tank 246.

At the completion of the first tank analysis, master timer 238, which drives stepping relay 222, pulses stepping relay 222 to contact point number 3. This allows relays 224 and 226 to open and sample valve 232 to close. Sample valves are attached to each of the other tanks in the system (not shown) in the same manner in which sample valve 232 is attached to etch tank 246 and are opened sequentially so that the purging, analysis and corrective action process for all tanks occur in the same manner as that described for the etch tank 246 shown. When the cycle has completed for all tanks, stepping relay 222 resets and the cycle repeats itself.

in summary, the present invention for the first time provides a method and its associated system for continuously, automatically analyzing and controlling etch solutions consisting of a container having a constant level control for the solution to be analyzed, and which includes a means of adding ingredients to or removing them from the container solution. The solution is automatically sampled responsive to an impulse from a stepping relay, treated with a standard solution and pumped through flow chambers where the pH valve is measured for both caustic and inhibitor simultaneously and independently the pH value then activating timer means to add caustic or delete inhibitor in the container in accordance with and responsive to the readings thus derived We claim:

1. A system for automatically controlling and maintaining the chemical concentrations effecting the etch rate of a caustic chemical-milling etchant-solution comprising:

A. means for containing an etchant solution; I

B. an adjusting drain operatively associated with each said etchant solution containing means, said drain normally closed;

C means for selectively sampling the etchant solution in each said etchant solution containing means;

D. means for containing a standard acid solution;

E. metering means associated with said acid containing means operative to neutralize an etchant sample from said etchant solution containing means and said acid solution containing means comprising first and second meters each comprising selectively constant flow dual metering pumps, said first meter operative to meter sufficient standard acid solution from said acid containing means to neutralize a first portion of the sample etchant solution for quantitative determination of the caustic therein, said second meter operative to meter sufficient standard acid solution from said acid containing means to neutralize a second portion of the sample etchant solution for quantitative determination of the inhibitor therein;

F. means for mixing the etchant sample and the standard acid solution and means operative to detect the equivalence point pH values associated with the caustic and inhibitor reactions resultant from said mixing of the etchant solution sample and standard acid solution;

1. said mixing means comprises a mixing chamber for each pH equivalence point value to be detected;

2. said detecting means comprises a pH meter for each said first and second meters, a first pH meter detecting a reduced caustic concentration through a first equivalence point value, and a second pH meter detecting any excess inhibitor through a second equivalence point;

G. adjusting means responsive to said detecting means comprising first and second solenoids, said first solenoid operative to cause addition of a metered amount of caustic to said etchant solution container responsive to the detection of a pH below a first equivalence point indicative of caustic deficiency, said second solenoid operative to open said adjusting drain to remove a metered amount of solution from said etchant solution container responsive to the detection of a pH value above a second equivalence point indicative of excess inhibitor.

2. A system for automatically controlling and maintaining the chemical concentration effecting the etch rate of a chemical milling etchant solution comprising:

A. a tank section comprising 1. means for containing an etchant solution having a constant level control responsive to the level of the etchant solution in said containing means;

2. an adjusting drain operatively associated with each said etchant solution containing means, said drain normally closed;

. a caustic reservoir selectively controlled by an addition valve which is in operative relationship to said etch solution containing means;

4. a water source in operative relationship to said etchant solution containing means, and said constant level control;

control section comprising a master timer;

a system programming means responsive to said master timer comprising a stepping relay operative to control a sampling cycle for each etchant solution containing means in the system;

3. means for selectively sampling the etchant solution in each said etchant containing means comprising a solenoid actuated sampling valve operatively connected to said etchant containing means and responsive to said stepping relay;

4. means for containing a standard acid solution;

5. metering means operatively associated with the said acid-containing means and said etchant solution sampling means operative to neutralize the etchant sample wherein said metering means comprises first and second dual-proportioning pumps, said first pump operative to continuously meter standard acid solution from said standard acid solution container to neutralize a first given portion of the sample etch solution for determination of a first equivalence point indicating caustic content, said second dual-proportioning pump means for mixing the sample etchant solution and standard acid solution comprising a mixing chamber for each said dual-proportioning pump operative to mix the etchant sample, standard acid solution and water;

. first and second timing means operatively associated with said addition valve and said adjusting drain responsive to a pH detecting means to determine the duration of the caustic addition and control flow therefrom;

. means operative to detect the equivalence point pH values of the caustic and inhibitor resultant from the mixing of the etch solution sample and standard acid solution, said means causing the addition of caustic if the first equivalence pH value indicates a caustic deficiency and opening said adjusting drain if the second equivalence pH value indicates an excess of inhibitor, said detecting means comprising a flow chamber in communication with each said mixing chamber, a pH meter operatively associated with each said flow chamber, a first of said pH meters measuring the pH of the sample solution from said first mixing chamber to determine a first equivalence point of the sample solution, a solenoid responsive to said first pH meter wherein, if the sample solution has less than a preset pH value indicating depletion of caustic, said first pH meter actuates said solenoid, actuating said first timer means to open said addition valve in said tank section, a second of said pH meters measuring the pH of the sample solution from said second mixing chamber to determine a second equivalence point of the sample solution indicating inhibitor buildup, a solenoid responsive to said second pH meter and operative to actuate said second timer means, said second timer means opening said tank section, adjusting drain for a preset period to reduce inhibitor buildup. 

2. said detecting means comprises a pH meter for each said first and second meters, a first pH meter detecting a reduced caustic concentration through a first equivalence point value, and a second pH meter detecting any excess inhibitor through a second equivalence point; G. adjusting means responsive to said detecting means comprising first and second solenoids, said first solenoid operative to cause addition of a metered amount of caustic to said etchant solution container responsive to the detection of a pH below a first equivalence point indicative of caustic deficiency, said second solenoid operative to open said adjusting drain to remove a metered amount of solution from said etchant solution container responsive to the detection of a pH value above a second equivalence point indicative of excess inhibitor.
 2. A system for automatically controlling and maintaining the chemical concentration effecting the etch rate of a chemical milling etchant solution comprising: A. a tank section comprising
 2. an adjusting drain operatively associated with each said etchant solution containing means, said drain normally closed;
 2. a system programming means responsive to said master timer comprising a stepping relay operative to control a sampling cycle for each etchant solution containing means in the system;
 3. means for selectively sampling the etchant solution in each said etchant containing means comprising a solenoid actuated sampling valve operatively connected to said etchant containing means and responsive to said stepping relay;
 3. a caustic reservoir selectiVely controlled by an addition valve which is in operative relationship to said etch solution containing means;
 4. a water source in operative relationship to said etchant solution containing means, and said constant level control; B. a control section comprising
 4. means for containing a standard acid solution;
 5. metering means operatively associated with the said acid-containing means and said etchant solution sampling means operative to neutralize the etchant sample wherein said metering means comprises first and second dual-proportioning pumps, said first pump operative to continuously meter standard acid solution from said standard acid solution container to neutralize a first given portion of the sample etch solution for determination of a first equivalence point indicating caustic content, said second dual-proportioning pump operative to continuously meter sufficient standard acid solution from said acid solution container to neutralize a second given portion of the caustic and inhibitor of the sample etch solution for determination of a second equivalence point indicating inhibitor content;
 6. means for mixing the sample etchant solution and standard acid solution comprising a mixing chamber for each said dual-proportioning pump operative to mix the etchant sample, standard acid solution and water;
 7. first and second timing means operatively associated with said addition valve and said adjusting drain responsive to a pH detecting means to determine the duration of the caustic addition and control flow therefrom;
 8. means operative to detect the equivalence point pH values of the caustic and inhibitor resultant from the mixing of the etch solution sample and standard acid solution, said means causing the addition of caustic if the first equivalence pH value indicates a caustic deficiency and opening said adjusting drain if the second equivalence pH value indicates an excess of inhibitor, said detecting means comprising a flow chamber in communication with each said mixing chamber, a pH meter operatively associated with each said flow chamber, a first of said pH meters measuring the pH of the sample solution from said first mixing chamber to determine a first equivalence point of the sample solution, a solenoid responsive to said first pH meter wherein, if the sample solution has less than a preset pH value indicating depletion of caustic, said first pH meter actuates said solenoid, actuating said first timer means to open said addition valve in said tank section, a second of said pH meters measuring the pH of the sample solution from said second mixing chamber to determine a second equivalence point of the sample solution indicating inhibitor buildup, a solenoid responsive to said second pH meter and operative to actuate said second timer means, said second timer means opening said tank section, adjusting drain for a preset period to reduce inhibitor buildup. 